N-polyhalovinylthioformamides

ABSTRACT

N-polyhalovinylthioformamides of the formula: WHEREIN R is hydrogen or alkyl of one to four carbon atoms, X is halogen of atomic number 17 to 35 and a is 2 or 3. These formamides are fungicidal, algicidal and nematocidal.

United States Patent Brown [451 Oct. 10, 1972 1 1 N- 3,178,447 4/1965 Kohn ..424/273 POLYHALOVINYLTHIOFORMAMIDES FOREIGN PATENTS OR APPLICATIONS [72] Inventor: Melancthon S. Brown, Berkeley,

Calif 1,317,400 1/ 1963 France ..260/453 [73] Assignee: Chevron Research Company, San P i E i L wi Gotts Francisco, Calif- Assistant Examiner--G. Hollrah 30 Att0rney-J. Buchanan, J12, G. E. Magdeburger,

[21] Appl. No.: 33,878

Related US. Application Data [63] Continuation-impart of Ser. No. 810,368,

March 25, 1969, abandoned, and a continuation-in-part of Ser. No. 748,642, June 30, 1968, abandoned.

[52] US. Cl ..260/453 R, 424/298, 11/66,

11/67, ll/98, 210/64, 162/161 [51] Int. Cl ..C07c 119/00 [58] Field of Search ..260/453 R; 424/320, 298

[56] References Cited UNITED STATES PATENTS 3,344,153 9/1967 Kuhle et al. ..260/453 John Stoner, Jr. and Raymond Owyang [57] ABSTRACT N-polyhalovinylthioformamides of the formula:

wherein R is hydrogen or alkyl of one to four carbon atoms, X is halogen of atomic number 17 to 35 and a is 2 or 3. These formamides are fungicidal, algicidal and nematocidal.

5 Claims, N0 Drawings N-POLYI-IALOVINYLTHIOFORMAMIDES CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of application Ser. No. 810,368, filed Mar. 25, 1969 now abandoned, and application Ser. No. 748,642, filed June 30, 1968 now abandoned. Application Ser. No. 810,368 is a continuation-in-part of application Ser. No. 748,642 and application Ser. No. 704,555, filed Feb. 12, 1968, now abandoned. Application Ser. No. 748,642 is a continuation-in-part of application Ser. No. 704,555. Related application Ser. No. 810,377 was filed Mar. 25, 1969 and is now abandoned.

FIELD OF THE INVENTION This invention concerns N-polyhalovinylthioformamides and their use as pesticides, especially as nematocides INVENTION DESCRIPTION The novel formamides of the present invention may be represented by the formula:

wherein R is hydrogen or alkyl of one to four carbon atoms, X is halogen of atomic number 17 to 35 and a is 2 or 3. Preferably X is chlorine and a is 3 and R is hydrogen.

Representative polyhalovinyl groups which -C X H may represent are trichlorovinyl, 1,2-dichlorovinyl, 2,2-dichlorovinyl, tribromovinyl, 2,2-dibromovinyl, 1,2-dibromovinyl, 2-bromo-2-chlorovinyl and the like.

Alkyl radicals which R may represent include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. The preferred alkyl groups are methyl and ethyl and more preferably methyl.

Typical formamides represented by the above formula are N-trichlorovinylthioformamide, N-tribromovinylthioformamide, N-2,2-dichlorovinylthioformamide, N-2,2-dibromovinylthioformamide, N-l,2-dichlorovinylthioformamide, N-methyl-N-trichlorovinylthioformamide, N-ethyl-N-trichlorovinylthioformamide, N- ethyl-N-tribromovinylthioformamide, N-propyl-N-1,2- dibromovinylthioformamide, and N-butyl-N-l-chloro- 2-bromovinylthioformamide.

The formamides of this invention may be prepared by reacting a sulfenyl halide with a primary formamide. This reaction is illustrated by the following chemical equation:

where R, X and a are as previously defined. It is desirable to carry out this reaction in the presence of inert solvents such as dimethyl sulfoxide, dimethylformamide, acetonitrile, dioxane and the like. The reaction temperature is, in general, not critical and will usually be in the range of about -20 to about 50 C., preferably about 0 to 20 C. Likewise, the pressure is not critical and will usually be atmospheric or autogenous. It is desirable to use stoichiometric proportions of the reactants or a slight excess of the sulfenyl halide reactant.

Forrnamides of this invention may also be prepared by dehydrohalogenating corresponding N-polyhaloalkylthioformamides. For instance, N- (tetrachloroethylthio) formamides may be dehydrochlorinated to produce N-trichlorovinylthioformamides. This dehydrohalogenation will normally be carried out at low temperatures, usually about 0 to 40 C. and in the presence of solvents such as benzene, toluene, ether, methylene chloride, acetonitrile and chloroform. Mild dehydrohalogenating agents such as tertiary amines (trialkyl amines, pyridine, etc.) or alkali metal carbonates will normally be employed. Triethylamine is a preferred agent.

EXAMPLES The following examples describe methods which may be used to prepare the formamides of this invention. These examples are not intended to limit the invention described herein. Percentages are by weight.

EXAMPLE 1 Fifteen g. of formamide and ml. of dimethylformamide were placed in a vessel and cooled in an ice bath. 25 g. trichlorovinylsulfenyl chloride was slowly added to the mixture. After this addition the vessel was removed from the ice bath and allowed to stand for one hour at ambient temperature with stirring. 750 ml. of ice water was then added to the vessel causing a precipitate to form. The precipitate was extracted in ethyl ether and washed with a sodium chloride solution, dried and then stripped. The solid was then dissolved in 50 ml. of hot hexane plus 35 ml. of hot benzene. The hexane-benzene solution was then cooled. The resulting solid product was filtered, washed in petroleum ether and dried. Chemical analysis of the N-trichlorovinylthioformamide was as follows:

15 g. of N-(1,1,2,2-tetrachloroethylthio) formamide and ml. acetonitrile were placed in a vessel cooled in an ice bath. 7 g. of triethylamine in 20 ml. acetonitrile was added dropwise to the vessel. After the addition was complete, the ice bath was removed and the reaction mixture was stirred at ambient temperature for 2 hours. The mixture was then cooled and fil tered. The acetonitrile was stripped from this filtrate and the stripped product was dissolved in about 500 ml. methylene chloride. This solution was washed with cold water and dried over MgSO It was then filtered and the methylene chloride was stripped from the filtrate leaving a solid cystalline residue. This residue was recrystallized twice from a mixture of hexane and benzene to give a small amount of N-trichlorovinylthioformamide. This compound was observed as a solid melting at 50-5 3 C. Its S and Cl analyses were:

Other formamides of this invention were prepared by the method described in Example 1. These formamides are listed in Table I.

The N-polyhalovinylthioformamides of this invention have exhibited biological activity against a variety of organisms, particularly fungi, algae and nematodes. Their activities against nematodes were unexpectedly better than those of the most closely related known formamides, the N-polyhaloalkylthioformamides. Also, many of them were significantly better fungicides and algicides than the known formamides.

The nematocidal activities of the formamides of this invention and their superiority over corresponding N- polyhaloalkylthio compounds were illustrated by testing representative amides of this invention and representative N-polyhaloalkylthio compounds by the following method. I

A 0.38 ml. portion of a 3% acetone solution of the test compound was diluted with 1 ml. acetone. The resulting solution was homogeneously mixed with 20 cc. of vermiculite. The treated vermiculite was then mixed homogeneously with 750 g. of soil, dry weight basis, which was severely infested with free-living nematodes (mixed culture of Meloidogyne javanica and Meloidogyne incognita). This mixing gave a concentration of approximately. 15 parts of the test compound per million parts of soil. This treated soil was stored for 4 days at 6575 F. It was then divided equally into 3 parts, each of which was put into a separate pot and kept for another 3 days. A 3-week old tomato (v.

Bonny Best) seedling was then transplanted into each TABLE II Compound Nematocidal Activity-'1:

N-trichlorovinylthioforrnamide l 00 N-methyl-N- trichlorovinylthioformarnide 96 N-2.2-dichlorovinylthioformamide 100 N-trichloromethylthioforrnamide 2 N- l l ,2,2-

tetrachloroethylthioformarnide 8 As illustrated above, the formamides of this invention may be used to control plant-parasitic nematodes by exposing them to a toxic amount of the formamide. Thus, these formamides will normally be applied to nematode-infested soil at dosages in the range of 3 to 40 lbs. per acre. They may be applied as liquid formulations by spraying or injection. The liquid formulations of these formamides maybe solutions, dispersions, or emulsions. Typical solvents which may be used are aromatics such as xylene, toluene and benzene, ketones such as cyclohexanone and the like. These liquid formulations will usually contain a wetting agent to facilitate the formamides penetration into the soil and generally enhance its effectiveness. They may also be applied as solid formulations containing carriers such as soil, sawdust, clay and the like. When used as a solid, these formamides will usually be plowed into the soil. Following their application to the soil, the soil will be watered to disperse the formamide below ground level.

Formamides of this invention are particularly useful for controlling organisms such as algae, bacteria, molds and occasionally aquatic weeds which foul aqueous industrial effluents and cooling streams, such as those occurring in the paper and food processing industriesa They may also be used to control such organisms in other aqueous bodies such as lakes, streams, canals, pools and the like. When so used, a biocidal quantity of one or more of the formamides of this invention is added to the aqueous growth environment of the organisms- Usually, this dosage will range between about 0.1 and 50 ppm. In any given instance, the optimum dosage will depend upon the particular organism and aqueous body involved. For instance, when used to control algae, these formamides will usually be employed at concentrations of about 0.1 to 10 ppm. In terms of pounds of formamide per acre of water 1 foot deep 0.1 to 10 ppm is equal toabout 0.3 to 30 lbs. per acre of water 1 foot deep. These formamides may be applied to the aqueous growth environments of such organisms as dispersible powders or in solution with water-miscible solvents.

Representative formamides of this invention were tested as algicides by the following method.

An acetate solution of equal parts of formamide and a surfactant was prepared. This solution was mixed with a nutrient broth in a quantity sufficient to give a concentration of 2 ppm formamide. Four repliace ml. specimen cups were filled with this mixture. 350-400 mg. of Euglena was added to each specimen cup and the cups were then placed in an environment chamber for incubation. The cups were observed periodicially for algae growth. The algicidal effectiveness of the formamide was determined based on a final observation of algae growth after 10 days.

TABLE III Compound Algicidal Effectiveness N-trichlorovinylthioformamide 100 N-methyl-N- trichlorovinylthioformamide 100 N-Z,Z-dichlorovinylthioformamide lOO Comparative algicidal testing indicated the formamides of this invention were more effective than corresponding N-polyhaloalkylthioformamides.

Formamides of this invention were also used to control fungi such as Pythium ultimum, Rhizoctonia solani, Fusarium oxysporum, f. phaseoli, Helminthosporium sativum, Verticillium alboatrum, Monilinia fructicola and Alternaria solani. When used as fungicides, the formamides of this invention will be formulated and applied in fungicidal amounts by conventional art methods to fungi or hosts which are subject to fungus attack, especially vegetative hosts such as plants, plant seeds, paper and the like. They may be combined with inert liquids and solids carriers as powders, solutions or dispersions for such use.

Pesticidal formulations of the formamides of this invention may also contain stabilizers, spreading agents, sticking agents, fillers, other compatible pesticides and the like.

As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

lclaim:

l. N-polyhalovinylthioformamides of the formula wherein R is hydrogen or alkyl of one to four carbon atoms, X is halogen of atomic number 17 to 35 and a is 2 or 3.

2. The formamides of claim 1 wherein R is hydrogen, methyl or ethyl.

3. The formamides of claim 1 wherein R is hydrogen.

4. The formamides of claim 1 wherein X is chlorine and a is 3.

5. The formamides of claim 1 wherein R is hydrogen, X is chlorine and a is 3. 

2. The formamides of claim 1 wherein R is hydrogen, methyl or ethyl.
 3. The formamides of claim 1 wherein R is hydrogen.
 4. The formamides of claim 1 wherein X is chlorine and a is
 3. 5. The formamides of claim 1 wherein R is hydrogen, X is chlorine and a is
 3. 